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Abstract:

In one aspect, the invention relates to azaporphyrins that are useful in
a variety of optical and electro-optical devices, including
photo-absorbing and emitting devices.

Claims:

1. A compound represented by the formula: ##STR00044## wherein M is
Zn2+, Cu2+, Pd2+, Pt2+, Fe2+, Co2+,
Ni2+, or Mg2+; Y1 and Y2 are independently N or
CR6, wherein R6 is optionally substituted aryl; R1 is
hydrogen or optionally substituted aryl; and each of R2, R3,
R4, and R5 independently comprises four substituents
independently selected from hydrogen, halide, and aryl, or wherein two
adjacent substituents form an optionally substituted aryl ring together
with the carbon to which they are attached, with the two other
substituents being selected from hydrogen, halide, and aryl.

2. The compound of claim 1, wherein the compound is not represented by
one or more of the formulae: ##STR00045## ##STR00046## ##STR00047##

3. The compound of claim 1, wherein each of R2, R3, R4,
and R5 independently comprises four hydrogens, provided that M is
not Zn, Cu, or Pd.

4. The compound of claim 1, wherein M is Zn2+, Cu2+, Pd2+,
or Pt2+.

5. The compound of claim 1, wherein one or more of Y1 or Y2 is
N.

6. The compound of claim 1, wherein R1 is hydrogen.

7. The compound of claim 1, wherein R1 is phenyl.

8. The compound of claim 1, wherein R1 is bromophenyl.

9. The compound of claim 1, wherein one or more of R2, R3,
R4, or R5 independently comprises two adjacent substituents
forming an optionally substituted aryl ring together with the carbon to
which they are attached, with the two other substituents being selected
from hydrogen, halide, and aryl.

10. The compound of claim 1, wherein one or more of R2, R3,
R4, and R5 independently comprises four hydrogens.

11. The compound of claim 1, wherein R6, when present, is phenyl.

12. The compound of claim 1, wherein R6, when present, is
bromophenyl.

Description:

BACKGROUND

[0001] 1. Technical Field

[0002] The present disclosure relates to azaporphyrins, and specifically
to π-conjugated azaporphyrins and methods of making and using such
azaporphyrins, including optical and electro-optical devices comprising
same.

[0003] 2. Technical Background

[0004] Organic compounds with delocalized conjugated π-electrons
exhibit unique optical properties and are relatively easy to process into
devices. Such compounds are thus ideally suited for use in a wide variety
of optical and electro-optical devices, including photo-absorbing devices
such as solar- and photo-sensitive devices, photo-emitting devices, such
as organic light emitting diodes (OLEDs), or devices capable of both
photo-absorption and emission. Much research has been devoted to the
discovery and optimization of organic materials for use in optical and
electro-optical devices. Generally, research in this area aims to
accomplish a number of goals, including improvements in absorption and
emission efficiency, as well as improvements in processing ability, among
others.

[0005] Despite significant advances in research devoted to optical and
electro-optical materials, many current devices comprising organic
materials have yet to be optimized. Many organic materials currently used
in optical and electro-optical devices have a number disadvantages,
including poor processing ability, inefficient emission or absorption,
and less than ideal stability, among others. Thus, a need exists for new
organic materials that can exhibit improved performance in optical and
electro-optical devices. This need and other needs are satisfied by the
compositions and methods of the present invention.

SUMMARY

[0006] In accordance with the purpose(s) of the invention, as embodied and
broadly described herein, this disclosure, in one aspect, relates to
azaporphyrins that can be useful in a variety of optical and
electro-optical devices.

[0007] In one aspect, the azaporphyrins disclosed herein are represented
by the following formula:

##STR00001##

wherein M is a transition metal, such as, for example, Zn2+,
Cu2+, Pd2+, Pt2+, Fe2+, Co2+, Ni2+, or
Mg2+; wherein Y1 and Y2 are independently N or CR6,
wherein R6 is optionally substituted aryl; wherein R1 is
hydrogen or optionally substituted aryl; and wherein each general "R"
group independently comprises an organic or inorganic residue, such as
alkyl, alkenyl, alkynyl, aryl, cyano, halogen, among others; wherein
----- is an optional bond, such that two adjacent "R" groups can form a
ring (such as an aryl) together with the carbon to which they are
attached.

[0008] In a further aspect, the azaporphyrin is represented by the
formula:

##STR00002##

wherein M is Zn2+, Cu2+, Pd2+, Pt.sup.+, Fe2+,
Co2+, Ni2+, or Mg2+; wherein Y1 and Y2 are
independently N or CR6, wherein R6 is optionally substituted
aryl; wherein R1 is hydrogen or optionally substituted aryl; and
wherein each of R2, R3, R4, and R5 independently
comprises four substituents independently selected from hydrogen, halide,
and aryl, or wherein two adjacent substituents form an optionally
substituted aryl ring together with the carbon to which they are
attached, with the two other substituents being selected from hydrogen,
halide, and aryl.

[0009] Also disclosed are optical and electro-optical devices comprising
the azaporphyrins of the present invention. In various aspects, light
emitting devices, photovoltaic devices, and solar devices, among others,
comprise one or more disclosed azaporphyrins.

BRIEF DESCRIPTION OF THE FIGURES

[0010] The accompanying figures, which are incorporated in and constitute
a part of this specification, illustrate several aspects and together
with the description serve to explain the principles of the invention.

[0011] FIGS. 1A-E show schematics of device applications of the disclosed
metal azaporphyrins: A) donor-type materials for photovoltaic cells; B)
absorbers for dye-sensitized solar cells; C) emitters for red and near
infra-red organic light emitting diodes; D) absorbers and re-emitters for
organic concentrators (i.e. a large area of organic film as collector of
sunlight for small-size and high efficiency inorganic PVs); E) absorbers
for a hydrogen generation system; all in accordance with the various
aspects of the present invention.

[0012] FIG. 2A shows an absorption spectrum of III-Zn-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0013]FIG. 2B shows a photoluminescence spectrum of III-Zn-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0014]FIG. 3A shows an absorption spectrum of I-Zn-2 in dichloromethane,
in accordance with the various aspects of the present invention.

[0015] FIG. 3B shows a photoluminescence spectrum of I-Zn-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0016]FIG. 4A shows an absorption spectrum of IV-Zn-2 in dichloromethane,
in accordance with the various aspects of the present invention.

[0017]FIG. 4B shows a photoluminescence spectrum of IV-Zn-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0018]FIG. 5A shows an absorption spectrum of III-H2-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0019]FIG. 5B shows a photoluminescence spectrum of III-H2-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0020]FIG. 6A shows an absorption spectrum of I-H2-2 in dichloromethane,
in accordance with the various aspects of the present invention.

[0021]FIG. 6B shows a photoluminescence spectrum of I-H2-2 in
dichloromethane, in accordance with the various aspects of the present
invention.

[0023] Additional aspects of the invention will be set forth in part in
the description which follows, and in part will be obvious from the
description, or can be learned by practice of the invention. The
advantages of the invention will be realized and attained by means of the
elements and combinations particularly pointed out in the appended
claims. It is to be understood that both the foregoing general
description and the following detailed description are exemplary and
explanatory only and are not restrictive of the invention, as claimed.

DESCRIPTION

[0024] The present invention can be understood more readily by reference
to the following detailed description of the invention and the Examples
included therein.

[0025] Before the present compounds, compositions, articles, systems,
devices, and/or methods are disclosed and described, it is to be
understood that they are not limited to specific synthetic methods unless
otherwise specified, or to particular reagents unless otherwise
specified, as such can, of course, vary. It is also to be understood that
the terminology used herein is for the purpose of describing particular
aspects only and is not intended to be limiting. Although any methods and
materials similar or equivalent to those described herein can be used in
the practice or testing of the present invention, example methods and
materials are now described.

DEFINITIONS

[0026] As used in the specification and the appended claims, the singular
forms "a," "an" and "the" include plural referents unless the context
clearly dictates otherwise. Thus, for example, reference to "an
azaporphyrin" includes mixtures of two or more azaporphyrins.

[0027] Ranges can be expressed herein as from "about" one particular
value, and/or to "about" another particular value. When such a range is
expressed, another aspect includes from the one particular value and/or
to the other particular value. Similarly, when values are expressed as
approximations, by use of the antecedent "about," it will be understood
that the particular value forms another aspect. It will be further
understood that the endpoints of each of the ranges are significant both
in relation to the other endpoint, and independently of the other
endpoint. It is also understood that there are a number of values
disclosed herein, and that each value is also herein disclosed as "about"
that particular value in addition to the value itself. For example, if
the value "10" is disclosed, then "about 10" is also disclosed. It is
also understood that each unit between two particular units are also
disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and
14 are also disclosed.

[0028] As used herein, the terms "optional" or "optionally" means that the
subsequently described event or circumstance can or can not occur, and
that the description includes instances where said event or circumstance
occurs and instances where it does not.

[0029] As used herein, the term "azaporphyrin" refers to a porphyrin
analog wherein at least one meso position is aza substituted, i.e.,
wherein a methine bridge (--CH--) (meso position) of a porphyrin is
substituted with a nitrogen atom (aza substitution). The azaporphyrin
derivatives can be monoazaporphyrins, diazaporphyrins, triazaporphyrins,
tetraazaporphyrins, or derivatives thereof, such as tetrabenzo-
substituted derivatives disclosed herein. The prefixes mono, di, tri, and
tetra, as used herein to modify "azaporphyrin," refer to the number of
aza substitutions at the meso position(s). Also included within the term
"azaporphyrins" are derivatives of azaporphyrins, which may not strictly
correspond to an azaporphyrin structure, but are structurally related.

[0030] A chemical term used herein to describe a compound or chemical
residue refers to the compound or residue regardless of whether the
compound or residue is actually obtained from the chemical species in the
chemical term used to describe the compound or residue. Thus, for
example, the term "azaporphyrin" does not imply that the compound in
reference was made from porphyrin. Likewise, a disclosed "derivative" or
"analog" only implies a relation, for example a structural relation,
between the derivative or analog and the chemical species or term used to
modify the term "derivative" or "analog." Thus, for example, an
"azaporphyrin derivative" does not imply that the azaporphyrin derivative
was derived from an azaporphyrin. However, it is understood that a
disclosed azaporphyrin derivative can, in some aspects, be derived from
an azaporphyrin.

[0031] As used herein, the term "substituted" is contemplated to include
all permissible substituents of organic compounds. In a broad aspect, the
permissible substituents include acyclic and cyclic, branched and
unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic
substituents of organic compounds. Illustrative substituents include, for
example, those described below. The permissible substituents can be one
or more and the same or different for appropriate organic compounds. For
purposes of this disclosure, the heteroatoms, such as nitrogen, can have
hydrogen substituents and/or any permissible substituents of organic
compounds described herein which satisfy the valences of the heteroatoms.
This disclosure is not intended to be limited in any manner by the
permissible substituents of organic compounds. Also, the terms
"substitution" or "substituted with" include the implicit proviso that
such substitution is in accordance with permitted valence of the
substituted atom and the substituent, and that the substitution results
in a stable compound, e.g., a compound that does not spontaneously
undergo transformation such as by rearrangement, cyclization,
elimination, etc.

[0032] An "optionally substituted" compound refers to a compound that can
be, but does not have to be, substituted with a substituent, such as
those described below or other substituents that are not specifically
disclosed but would not interfere with the desired function of the
compound.

[0033] The term "alkyl" as used herein is a branched or unbranched
saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl,
n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,
decyl, dode cyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the
like. The alkyl group can be cyclic or acyclic. The alkyl group can be
branched or unbranched. The alkyl group can also be substituted or
unsubstituted. For example, the alkyl group can be substituted with one
or more groups including, but not limited to, optionally substituted
alkyl, cycloalkyl, alkoxy, amino, ether, halide, hydroxy, nitro, silyl,
sulfo-oxo, or thiol, as described herein. A "lower alkyl" group is an
alkyl group containing from one to six (e.g., from one to four) carbon
atoms.

[0034] "Alkyl" is generally used to refer to both unsubstituted alkyl
groups and substituted alkyl groups; however, substituted alkyl groups
are also specifically referred to herein by identifying the specific
substituent(s) on the alkyl group. For example, the term "halogenated
alkyl" specifically refers to an alkyl group that is substituted with one
or more halide, e.g., fluorine, chlorine, bromine, or iodine. The term
"alkoxyalkyl" specifically refers to an alkyl group that is substituted
with one or more alkoxy groups, as described below. The term "alkylamino"
specifically refers to an alkyl group that is substituted with one or
more amino groups, as described below, and the like. When "alkyl" is used
in one instance and a specific term such as "alkylalcohol" is used in
another, it is not meant to imply that the term "alkyl" does not also
refer to specific terms such as "alkylalcohol" and the like.

[0035] This practice is also used for other groups described herein. That
is, while a term such as "cycloalkyl" refers to both unsubstituted and
substituted cycloalkyl moieties, the substituted moieties can, in
addition, be specifically identified herein; for example, a particular
substituted cycloalkyl can be referred to as, e.g., an "alkylcycloalkyl."
Similarly, a substituted alkoxy can be specifically referred to as, e.g.,
a "halogenated alkoxy," a particular substituted alkenyl can be, e.g., an
"alkenylalcohol," and the like. Again, the practice of using a general
term, such as "cycloalkyl," and a specific term, such as
"alkylcycloalkyl," is not meant to imply that the general term does not
also include the specific term.

[0036] The term "cycloalkyl" as used herein is a non-aromatic carbon-based
ring composed of at least three carbon atoms. Examples of cycloalkyl
groups include, but are not limited to, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, norbornyl, and the like. The term
"heterocycloalkyl" is a type of cycloalkyl group as defined above, and is
included within the meaning of the term "cycloalkyl," where at least one
of the carbon atoms of the ring is replaced with a heteroatom such as,
but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The
cycloalkyl group and heterocycloalkyl group can be substituted or
unsubstituted. The cycloalkyl group and heterocycloalkyl group can be
substituted with one or more groups including, but not limited to,
optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halide,
hydroxy, nitro, silyl, sulfo-oxo, or thiol as described herein.

[0037] The terms "alkoxy" and "alkoxyl" as used herein to refer to an
alkyl or cycloalkyl group bonded through an ether linkage; that is, an
"alkoxy" group can be defined as --OA1 where A1 is alkyl or
cycloalkyl as defined above. "Alkoxy" also includes polymers of alkoxy
groups as just described; that is, an alkoxy can be a polyether such as
--OA1-OA2 or --OA1-(OA2)a-OA3, where "a" is
an integer of from 1 to 200 and A1, A2, and A3 are alkyl
and/or cycloalkyl groups.

[0038] The term "alkenyl" as used herein is a hydrocarbon group of from 2
to 24 carbon atoms with a structural formula containing at least one
carbon-carbon double bond. Asymmetric structures such as
(A1A2)C═C(A3A4) are intended to include both the
E and Z isomers. This can be presumed in structural formulae herein
wherein an asymmetric alkene is present, or it can be explicitly
indicated by the bond symbol C═C. The alkenyl group can be
substituted with one or more groups including, but not limited to,
optionally substituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl,
alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic
acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl,
sulfo-oxo, or thiol, as described herein.

[0039] The term "cycloalkenyl" as used herein is a non-aromatic
carbon-based ring composed of at least three carbon atoms and containing
at least one carbon-carbon double bound, i.e., C═C. Examples of
cycloalkenyl groups include, but are not limited to, cyclopropenyl,
cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl,
cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl"
is a type of cycloalkenyl group as defined above, and is included within
the meaning of the term "cycloalkenyl," where at least one of the carbon
atoms of the ring is replaced with a heteroatom such as, but not limited
to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkenyl group and
heterocycloalkenyl group can be substituted or unsubstituted. The
cycloalkenyl group and heterocycloalkenyl group can be substituted with
one or more groups including, but not limited to, optionally substituted
alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,
aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,
hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described
herein.

[0040] The term "alkynyl" as used herein is a hydrocarbon group of 2 to 24
carbon atoms with a structural formula containing at least one
carbon-carbon triple bond. The alkynyl group can be unsubstituted or
substituted with one or more groups including, but not limited to,
optionally substituted alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl,
alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic
acid, ester, ether, halide, hydroxy, ketone, azide, nitro, silyl,
sulfo-oxo, or thiol, as described herein.

[0041] The term "cycloalkynyl" as used herein is a non-aromatic
carbon-based ring composed of at least seven carbon atoms and containing
at least one carbon-carbon triple bound. Examples of cycloalkynyl groups
include, but are not limited to, cycloheptynyl, cyclooctynyl,
cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of
cycloalkenyl group as defined above, and is included within the meaning
of the term "cycloalkynyl," where at least one of the carbon atoms of the
ring is replaced with a heteroatom such as, but not limited to, nitrogen,
oxygen, sulfur, or phosphorus. The cycloalkynyl group and
heterocycloalkynyl group can be substituted or unsubstituted. The
cycloalkynyl group and heterocycloalkynyl group can be substituted with
one or more groups including, but not limited to, optionally substituted
alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl,
aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide,
hydroxy, ketone, azide, nitro, silyl, sulfo-oxo, or thiol as described
herein.

[0042] The term "aryl" as used herein is a group that contains any
carbon-based aromatic group including, but not limited to, benzene,
naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term
"aryl" also includes "heteroaryl," which is defined as a group that
contains an aromatic group that has at least one heteroatom incorporated
within the ring of the aromatic group. Examples of heteroatoms include,
but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
Likewise, the term "non-heteroaryl," which is also included in the term
"aryl," defines a group that contains an aromatic group that does not
contain a heteroatom. The aryl group can be substituted or unsubstituted.
The aryl group can be substituted with one or more groups including, but
not limited to, optionally substituted alkyl, cycloalkyl, alkoxy,
alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde,
amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, azide,
nitro, silyl, sulfo-oxo, or thiol as described herein. The term "biaryl"
is a specific type of aryl group and is included in the definition of
"aryl." Biaryl refers to two aryl groups that are bound together via a
fused ring structure, as in naphthalene, or are attached via one or more
carbon-carbon bonds, as in biphenyl.

[0043] The term "aldehyde" as used herein is represented by the formula
--C(O)H. Throughout this specification "C(O)" is a short hand notation
for a carbonyl group, i.e., C═O.

[0044] The terms "amine" or "amino" as used herein are represented by the
formula NA1A2A3, where A1, A2, and A3 can
be, independently, hydrogen or optionally substituted alkyl, cycloalkyl,
alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group
as described herein.

[0045] The term "carboxylic acid" as used herein is represented by the
formula --C(O)OH.

[0046] The term "ester" as used herein is represented by the formula
--OC(O)A1 or --C(O)OA1, where A1 can be an optionally
substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein. The term
"polyester" as used herein is represented by the formula
-(A1O(O)C-A2-C(O)O)a-- or
-(A1O(O)C-A2-OC(O))a--, where A1 and A2 can be,
independently, an optionally substituted alkyl, cycloalkyl, alkenyl,
cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described
herein and "a" is an integer from 1 to 500. "Polyester" is as the term
used to describe a group that is produced by the reaction between a
compound having at least two carboxylic acid groups with a compound
having at least two hydroxyl groups.

[0047] The term "ether" as used herein is represented by the formula
A1OA2, where A1 and A2 can be, independently, an
optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group described herein. The term
"polyether" as used herein is represented by the formula
-(A1O-A2O)a--, where A1 and A2 can be,
independently, an optionally substituted alkyl, cycloalkyl, alkenyl,
cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described
herein and "a" is an integer of from 1 to 500. Examples of polyether
groups include polyethylene oxide, polypropylene oxide, and polybutylene
oxide.

[0048] The term "halide" as used herein refers to the halogens fluorine,
chlorine, bromine, and iodine.

[0049] The term "heterocycle," as used herein refers to single and
multi-cyclic aromatic or non-aromatic ring systems in which at least one
of the ring members is other than carbon. Heterocycle includes pyridinde,
pyrimidine, furan, thiophene, pyrrole, isoxazole, isothiazole, pyrazole,
oxazole, thiazole, imidazole, oxazole, including, 1,2,3-oxadiazole,
1,2,5-oxadiazole and 1,3,4-oxadiazole,thiadiazole, including,
1,2,3-thiadiazole, 1,2,5-thiadiazole, and 1,3,4-thiadiazole, triazole,
including, 1,2,3-triazole, 1,3,4-triazole, tetrazole, including
1,2,3,4-tetrazole and 1,2,4,5-tetrazole, pyridine, pyridazine,
pyrimidine, pyrazine, triazine, including 1,2,4-triazine and
1,3,5-triazine, tetrazine, including 1,2,4,5-tetrazine, pyrrolidine,
piperidine, piperazine, morpholine, azetidine, tetrahydropyran,
tetrahydrofuran, dioxane, and the like.

[0050] The term "hydroxyl" as used herein is represented by the formula
--OH.

[0051] The term "ketone" as used herein is represented by the formula
A1C(O)A2, where A1 and A2 can be, independently, an
optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein.

[0052] The term "azide" as used herein is represented by the formula
--N3.

[0053] The term "nitro" as used herein is represented by the formula
--NO2.

[0054] The term "nitrile" as used herein is represented by the formula
--CN.

[0055] The term "silyl" as used herein is represented by the formula
--SiA1A2A3, where A1, A2, and A3 can be,
independently, hydrogen or an optionally substituted alkyl, cycloalkyl,
alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl
group as described herein.

[0056] The term "sulfo-oxo" as used herein is represented by the formulas
--S(O)A1, --S(O)2A1, --OS(O)2A1, or
--OS(O)2OA1, where A1 can be hydrogen or an optionally
substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein. Throughout
this specification "S(O)" is a short hand notation for S═O. The term
"sulfonyl" is used herein to refer to the sulfo-oxo group represented by
the formula --S(O)2A1, where A1 can be hydrogen or an
optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein. The term
"sulfone" as used herein is represented by the formula
A'S(O)2A2, where A1 and A2 can be, independently, an
optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein. The term
"sulfoxide" as used herein is represented by the formula
A1S(O)A2, where A1 and A2 can be, independently, an
optionally substituted alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl,
cycloalkynyl, aryl, or heteroaryl group as described herein.

[0057] The term "thiol" as used herein is represented by the formula --SH.

[0058] The term "organic residue" defines a carbon containing residue,
i.e., a residue comprising at least one carbon atom, and includes but is
not limited to the carbon-containing groups, residues, or radicals
defined hereinabove. Organic residues can contain various heteroatoms, or
be bonded to another molecule through a heteroatom, including oxygen,
nitrogen, sulfur, phosphorus, or the like. Examples of organic residues
include but are not limited alkyl or substituted alkyls, alkoxy or
substituted alkoxy, mono or di-substituted amino, amide groups, etc.
Organic residues can preferably comprise 1 to 18 carbon atoms, 1 to 15,
carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon
atoms, or 1 to 4 carbon atoms. In a further aspect, an organic residue
can comprise 2 to 18 carbon atoms, 2 to 15, carbon atoms, 2 to 12 carbon
atoms, 2 to 8 carbon atoms, 2 to 4 carbon atoms, or 2 to 4 carbon atoms.

[0059] One or more of the above described chemical terms may not be
specifically referenced in the context of a disclosed compound, but it is
contemplated that one or more of the above defined groups can be present
as a substituent on a disclosed compound, unless the context clearly
dictates otherwise.

[0060] Disclosed are the components to be used to prepare the compositions
of the invention as well as the compositions themselves to be used within
the methods disclosed herein. These and other materials are disclosed
herein, and it is understood that when combinations, subsets,
interactions, groups, etc. of these materials are disclosed that while
specific reference of each various individual and collective combinations
and permutation of these compounds can not be explicitly disclosed, each
is specifically contemplated and described herein. For example, if a
particular compound is disclosed and discussed and a number of
modifications that can be made to a number of molecules including the
compounds are discussed, specifically contemplated is each and every
combination and permutation of the compound and the modifications that
are possible unless specifically indicated to the contrary. Thus, if a
class of molecules A, B, and C are disclosed as well as a class of
molecules D, E, and F and an example of a combination molecule, A-D is
disclosed, then even if each is not individually recited each is
individually and collectively contemplated meaning combinations, A-E,
A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise,
any subset or combination of these is also disclosed. Thus, for example,
the sub-group of A-E, B-F, and C-E would be considered disclosed. This
concept applies to all aspects of this application including, but not
limited to, steps in methods of making and using the compositions of the
invention. Thus, if there are a variety of additional steps that can be
performed it is understood that each of these additional steps can be
performed with any specific embodiment or combination of embodiments of
the methods of the invention.

[0061] In one aspect, the present invention relates to azaporphyrins which
are useful as components of an optical or electro-optical device. The
disclosed azaporphyrins exhibit a variety of useful properties, including
for example, efficient absorption, emission, or absorption and emission,
making them ideally suited for use in an optical or electro-optical
device. In one aspect, the disclosed compounds are hybrids of
porphyrin-based compounds and phthalocyanines
(tetrabenzotetranzaporphyrin), and as such exhibit a variety of
advantages unique to both porphyrins and phthalocyanines, including even
synergistic advantages unrealized with a porphyrin or phthalocyanine
alone. For example, the disclosed azaporphyrins show strong absorption in
the visible region of the electromagnetic spectrum, as exhibited by many
phthalocyanines. Additionally, the disclosed azaporphyrins are also
highly emissive, much like many porphyrin-based compounds. It follows
that the disclosed azaporphyrins are ideally suited for use in a wide
range of applications, including without limitation light emitting
diodes, organic thin solar cells, dye-sensitized solar cells, organic
concentrators, and solar hydrogen generation systems, as discussed
herein.

[0062] The azaporphyrins disclosed herein can be monoazaporphyrins,
diazaporphyrins, triazaporphyrins, tetranzaporphyrins, or derivatives
thereof, including for example, benzoazapoiphyrins. Generally, the
compounds are represented by the following formula:

##STR00003##

wherein M is a transition metal, such as Zn2+, Cu2+, Pd2+,
Pt2+, Fe2+, Co2+, Ni2+, or Mg2+; wherein Y1
and Y2 are independently N or CR6, wherein R6 is
optionally substituted aryl; wherein R1 is hydrogen or optionally
substituted aryl; and wherein each general "R" group independently
comprises an organic or inorganic residue, such as alkyl, alkenyl,
alkynyl, aryl, cyano, halogen, among others; wherein is an optional bond,
such that two adjacent "R" groups can form a ring (such as an aryl)
together with the carbon to which they are attached.

[0063] In a further aspect, the azaporphyrin is a tetrabenzoazaporphyrin.
Examples of tetrabenzoazaporphrins include without limitation
tetrabenzomonoazaporphyrin, tetrabenzodiazaporphyrin,
tetrabenzotriazaporphyrin, tetrabenzotetranzaporphyrin (also known as
Phthalocyanine), and derivatives thereof. Exemplary
tetrabenzoazaporphyrins are represented by the following formula:

##STR00004##

wherein M is Zn2+, Cu2+, Pd2+, Pt2+, Fe2+,
Co2+, Ni2+, or Mg2+; wherein Y1 and Y2 are
independently N or CR6, wherein R6 is optionally substituted
aryl; wherein R1 is hydrogen or optionally substituted aryl; and
wherein each of R2, R3, R4, and R5 independently
comprises four substituents independently selected from hydrogen, halide,
and aryl, or wherein two adjacent substituents form an optionally
substituted aryl ring together with the carbon to which they are
attached, with the two other substituents being selected from hydrogen,
halide, and aryl.

[0064] In a specific aspect, the azaporphryin comprises one or more of
Zn2+, Cu2+, Pd2+, or Pt2+. For example, in the
formulae above or below, M can be Zn2+, Cu2+, Pd2+, or
Pt2+. In a further aspect of a disclosed azaporphyrin formula, one
or more of Y1 or Y2 is N. Thus, as described above, if one of
Y1 or Y2 is N, the compound is a diazaporphyrin. Likewise, if
both of Y1 and Y2 are N, the compound is a triazaporphyrin, and
so on. In another specific aspect, R1 is hydrogen. In a different
aspect, R1 is phenyl, for example bromophenyl.

[0065] In other specific aspects, one or more of R2, R3,
R4, or R5 independently comprises two adjacent substituents
forming an optionally substituted aryl ring together with the carbon to
which they are attached, with the two other substituents on the
benzo-ring being selected from hydrogen, halide, and aryl. In a different
aspect, one or more of R2, R3, R4, and R5
independently comprises four hydrogens.

[0066] In a further aspect, when CR6 is present as Y1 or Y2
or both, R6 can comprise a variety of substituents, such as aryl. In
one aspect, R6 is phenyl, such as, for example, bromophenyl.

[0067] In one aspect, the azaporphyrin is represented by one or more of
the following formulae:

##STR00005## ##STR00006##

[0068] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00007##

[0069] In another specific aspect, the azaporphyrin is represented by:

##STR00008##

, wherein M comprises zinc.

[0070] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00009## ##STR00010##

[0071] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00011## ##STR00012##

[0072] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00013## ##STR00014##

[0073] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00015## ##STR00016##

[0074] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00017## ##STR00018## ##STR00019##

[0075] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

##STR00020## ##STR00021## ##STR00022##

[0076] In another aspect, the azaporphyrin is represented by one or more
of the following formulae:

[0088] In a further aspect of a formula above, each of R2, R3,
R4, and R5 independently comprises four hydrogens, provided
that M is not Zn, Cu, or Pd.

[0089] The disclosed azaporphyrins can be made using a variety of
synthetic protocols, either known or disclosed herein. Exemplary
synthetic methods generally start with a reaction of one or more of the
four corner π-congugated groups of the azaporphyrin. Suitable starting
materials for forming the azaporphyrin ring or precursor therefore
include without limitation phthalic acid, phthalonitrile,
o-cyanobenzamide, phthalanhydride, phthalimide, diiminoisoindole,
including derivatives and combinations thereof. From these starting
materials or other starting materials, the azaporphyrin ring can be
provided using a one-pot method (i.e. wherein the ring is fully formed)
or a step-wise method (i.e. wherein each corner of the azaporphyrin is in
a sequence).

[0090] In some aspects, the azaporphyrin is provided by reacting an amine
or imine containing compound, such as an indole or other starting
material discussed above, with a corresponding acid, activated ester, or
other suitable electrophile to provide the imine (or aza functionality).
This protocol can be used to provide the azaporphyrin in a one-pot
reaction. In another aspect, a dimer formed during such a reaction can be
further reacted with itself to form the fully cyclized azaporphryin. In
some aspects, it can be preferable to perform the cyclization reaction
under dilute conditions (thermodynamic conditions) so as not to induce
unwanted kinetic reactions producing trimers, oligimers, and the like. A
metal can be inserted during or after the formation of the azaporphyrin
ring using metal insertion reactions, such as oxidation or reduction
reactions. In some aspects, an inserted metal can be exchanged with
another metal to provide a different metal center using a further metal
insertion or exchange reaction.

[0091] In another aspect, an azaporphyrin or the products of an
azaporphyrin synthesis procedure can optionally be subjected to one or
more purification steps, such as, for example, a chromatographic
separation. In such an aspect, one or more desired azaporphyrin products
can be separated and/or optionally isolated from any other reaction
products or byproducts that may be present.

[0092] The disclosed azaporphyrins, as discussed above, can be used in a
variety of applications, including without limitation optical and
electro-optical devices. Exemplary devices include without limitation
light emitting diodes, organic thin solar cells, dye-sensitized solar
cells, organic concentrators, and solar hydrogen generation systems. In
one aspect, a disclosed azaporphyrin can be used a portion of an organic
thin solar cell. In one aspect, a disclosed azaporphyrin can be used a
portion of a dye-sensitized solar cell. In one aspect, a disclosed
azaporphyrin can be used a portion of an organic concentrator. In one
aspect, a disclosed azaporphyrin can be used a portion of a solar
hydrogen generation system. In another aspect, a disclosed azaporphyrin
can form a light emitting layer or a portion thereof. In another aspect,
a disclosed azaporphyrin can form a light absorbing layer or a portion
thereof. It should be appreciated that other components can optionally be
mixed with or used in a same layer as an azaporphyrin. It should also be
appreciated that other layers can optionally be provided in a device, and
one of skill in the art could readily select an appropriate composition
for such a device. The disclosed azaporphyrins can be processed into such
a device using methods known in the art. In one aspect, any processing
method for incorporating an azaporphyrin of the present invention into a
device does not damage or adversely affect the light absorbing or light
emitting properties of the azaporphyrin. Depending on the desired
application, the disclosed azaporphyrins can be attached to a surface,
e.g. covalently attached, or polymerized together to afford a polymer
which can in some aspects provide for a better ability to process the
azaporphyrin into a device.

[0093] With reference to FIGS. 1A-1E, a variety of general device
schematics are shown, comprising exemplary azaporphyrins disclosed
herein. With reference to FIG. 1A, a polymer of a disclosed azaporphyrin
can be used as a charge donor-type material for a photovoltaic cell. With
reference to FIG. 1B, a disclosed azaporphyrin can be covalently attached
to a surface and used as a photon-absorbing material for a solar cell,
such as a dye-sensitized solar cell. With reference to FIG. 1C, a
disclosed azaporphyrin can be used as the emitting material for an
organic light emitting diode, such as a red or near infra-red organic
light emitting diode. With reference to FIG. 1D, a disclosed azaporphyrin
can be used as both an absorber and re-emitter for an organic light
concentrator (e.g., as a large area of a collector of sunlight for
small-size and high efficiency inorganic photovoltaics). With reference
to FIG. 1E, a disclosed azaporphyrin can be used as an absorber for a
hydrogen generation system or other catalytic system.

[0094] As can be seen from FIGS. 2A-4B, exemplary azaporphyrins disclosed
herein exhibit useful optical properties, including without limitation,
strong absorption in a variety of spectral regions, including blue, red,
and infra-red regions. It will be apparent that the absorption properties
of the disclosed azaporphyrins is related to the electronic structure of
the azaporphyrin, which can be modulated through the introduction of
various functional groups (such as electron withdrawing or donating
groups) at a variety of locations of the azaporphyrin ring, in addition
to changing the metal center. As an example, the azaporphyrin shown in
FIGS. 2A and 2B, which is a diphenyl substituted
diazatetrabenzoporphyrin, exhibits strong absorption and emission near
the red region of the spectrum, while the azaporphyrin shown in FIGS. 3A
and 3B, which is a triphenyl monoazatetrabenzoporphyrin, exhibits two
strong absorption peaks in the blue and near-red regions and emission in
the near-red to red region. The ability to tailor the absorption and
emission of the disclosed azaporphyrins allows for the design of
different compounds for different optical and electro-optical
applications. As a reference and control for the exemplary azaporphyrins
shown in FIGS. 2A-4B, FIGS. 5A-6B show absorption and emission spectra of
un-metallated azaporphryn rings.

[0095] In one aspect, an azaporphyrin can comprise a plurality of a single
type of azaporphyrin. In other aspects, an azaporphyrin composition can
comprise a mixture of two or more different azaporphyrins. In another
aspect, multiple different azaporphyrins can be combined so as to, for
example, absorb and/or emit light at a variety of wavelengths.

EXAMPLES

[0096] The following examples are put forth so as to provide those of
ordinary skill in the art with a complete disclosure and description of
how the compounds, compositions, articles, devices and/or methods claimed
herein are made and evaluated, and are intended to be purely exemplary of
the invention and are not intended to limit the scope of what the
inventors regard as their invention. Efforts have been made to ensure
accuracy with respect to numbers (e.g., amounts, temperature, etc.), but
some errors and deviations should be accounted for. Unless indicated
otherwise, parts are parts by weight, temperature is in ° C. or is
at ambient temperature, and pressure is at or near atmospheric.

[0097] 1. Synthesis: Exemplary Class of Azaporphyrins

##STR00041## ##STR00042## ##STR00043##

[0098] 2. Synthesis of III-Zn-2:

[0099] A mixture of phthalimide (6 g), phenylacetic acid (5 g), and zinc
oxide (3.2 g) was kept at 250° C. for 1 h, after which the melt
was cooled, ground, and boiled in 100 mL of 10% HCl for 5 min. The
precipitate was filtered off and washed with 200 mL of hot water. The
dried solid was purified by chromatograph. The main red band was
collected to produce intermediate. This intermediate was treated with
p-toluenesulfuric acid and HMDS (2 eq.) for 10 hours under 110° C.
1,3-diiminoisoindoline (4 eq.), zinc oxide (2 eq.) were added into
mixture, and the mixture was heated to 280° C. and kept for 10 h.
The solid was cooled, ground, and washed by 100 mL of 10% HCl and then
water. The precipitate was purified by chromatograph to produce III-Zn-2:
1H NMR (CDCl3): 9.45 (d, 2H), 9.29 (dd, 2H), 8.14 (d, 4H),
8.01-8.06 (m, 4H), 7.91-7.95 (m, 4H), 7.85 (dd, 2H), 7.57 (dd, 2H), 7.35
(dd, 2H), 7.10 (dd, 2H), 6.84 (d, 2H).

[0103] A solution of 0.2 g of I-Zn-2 in 25 mL of sulfuric acid was allowed
to stand at room temperature for 1 day and then poured into 100 ml of
ice-water. The precipitate that formed was filtered off, washed with
water to neutral washings. The residue was dried and purified by
chromatography to form I-H2-2. I-H2-2 and platinum(II) chloride (2 eq.)
was resolved in DMSO. The mixture was heated to 120° C., and stand
for 1 day, then poured into 100 mL of water. The precipitate that formed
was filtered off, washed with water, and purified by chromatography to
form 1-Pt-2. 1H NMR (500 MHz, CDCl3) 9.55 (d, 2H), 8.24-8.26
(m, 6H), 7.97-8.02 (m, 6H), 7.91 (dd, 4H), 7.88 (t, 2H), 7.29-7.33 (m,
4H), 7.20 (d, 2H), 7.15 (d, 2H), 7.05 (d, 2H).

[0104] 5. Analysis of IV-Zn-2:

[0105] In another example, a device was assembled comprising an indium tin
oxide (ITO) substrate, a layer of Zinc triazatetrabenzoporphyrin
(W-Zn-2), as described above, with a thickness between 5 nm and 20 nm, a
30 nm layer of C60, a 10 nm layer of (dihexyl-perylene tetracarboxylic
diimide (PTCDI), a 14 nm layer of bathocuproine (BCP), and an aluminum
layer. The current voltage characteristics of the device were then
measured under 1 sun condition (AM1.5@ 100 mW/cm2), the results of
which are illustrated in FIG. 7. This data illustrates the suitability of
the inventive azaporphyrin compounds as absorbers for organic
photovoltaics applications.

[0106] It will be apparent to those skilled in the art that various
modifications and variations can be made in the present invention without
departing from the scope or spirit of the invention. Other embodiments of
the invention will be apparent to those skilled in the art from
consideration of the specification and practice of the invention
disclosed herein. It is intended that the specification and examples be
considered as exemplary only, with a true scope and spirit of the
invention being indicated by the following claims.